Microcrystalline Cellulose Compositions

ABSTRACT

Ultra-fine microcrystalline cellulose compositions are disclosed which comprise co-attrited microcrystalline cellulose and a hydrocolloid. The compositions have a mean particle size of less than 10 microns. The compositions are prepared by subjecting a high solids mixture of microcrystalline cellulose and a hydrocolloid to high shear forces in the presence of an anti slip agent preferably an aqueous solution of an inorganic salt. The compositions are especially useful in food, pharmaceutical and cosmetic and industrial applications.

The present invention relates to microcrystalline cellulosecompositions, to a process for their manufacture, and to productscontaining the same. More particularly the invention relates toparticulate microcrystalline cellulose compositions having a meanparticle size of less than about 10 microns and comprising closely boundmicrocrystalline cellulose and at least one hydrocolloid. Thecompositions are prepared by applying a shear force to a high solidsmixture of microcrystalline cellulose and a hydrocolloid by vigorouslykneading the mixture in the presence of an anti-slip agent.

BACKGROUND OF THE INVENTION

Microcrystalline cellulose (MCC) is a white, odorless, tasteless,relatively free flowing, crystalline powder that is virtually free fromorganic and inorganic contaminants. It is a purified, partiallydepolymerized cellulose obtained by subjecting alpha cellulose obtainedas a pulp from fibrous plant material to hydrolytic degradationtypically with mineral acid. It is a highly crystalline particulatecellulose consisting primarily of crystalline aggregates which areobtained by removing amorphous (fibrous cellulose) regions of acellulosic material. MCC is used in a variety of applications includingfoods, pharmaceuticals and cosmetics.

Microcrystalline cellulose may be produced by treating a source ofcellulose, preferably alpha cellulose in the form of pulp from fibrousplant materials, with a mineral acid, preferably hydrochloric acid. Theacid selectively attacks the less ordered regions of the cellulosepolymer chain thereby exposing and freeing the crystalline sites whichform crystallite aggregates which constitute the microcrystallinecellulose. These are then separated from the reaction mixture, andwashed to remove degraded by-products. The resulting wet mass, generallycontaining 40 to 60 percent moisture, is referred to in the art byseveral names, including hydrolyzed cellulose, hydrolyzed cellulosewetcake, level-off DP cellulose, microcrystalline cellulose wetcake orsimply wetcake.

When the wetcake is dried and freed of water the resulting product,microcrystalline cellulose, is a white, odorless, tasteless, relativelyfree-flowing powder, insoluble in water, organic solvents, dilutealkalis and acids. For a description of microcrystalline cellulose andits manufacture see U.S. Pat. No. 2,978,446. The patent describes itsuse as a pharmaceutical excipient, particularly as a binder,disintegrant, flow aid, and/or filler for preparation of compressedpharmaceutical tablets.

Microcrystalline cellulose and/or hydrolyzed cellulose wetcake has beenmodified for other uses, notably for use as a gelling agent for foodproducts, a thickener for food products, a fat substitute and/ornon-caloric filler for various food products, as a suspension stabilizerand/or texturizer for food products, and as an emulsion stabilizer andsuspending agent in pharmaceutical and cosmetic lotions and creams.Modification for such uses is carried out by subjectingmicro-crystalline cellulose or wetcake to intense attrition forces as aresult of which the crystallites are substantially subdivided to producefinely divided particles. However, as particle size is diminished, theindividual particles tend to agglomerate or hornify upon drying,probably due to hydrogen or other bonding forces between the smallersized particles. To prevent agglomeration or hornification, a protectivecolloid, such as sodium carboxy-methylcellulose (CMC), which wholly orpartially neutralizes the bonding forces which cause agglomeration orhornification, may be added during attrition or following attrition butbefore drying. This additive also facilitates re-dispersion of thematerial following drying. The resulting material is frequently referredto as attrited microcrystalline cellulose or colloidal microcrystallinecellulose. For a description of colloidal microcrystalline cellulose,its manufacture and uses, see U.S. Pat. No. 3,539,365.

Colloidal microcrystalline cellulose is a white odorless, hygroscopicpowder. On being dispersed in water, it forms white, opaque thixotropicgels with microcrystalline cellulose particles less than 1 micron insize. It is manufactured and sold by FMC Corporation (FMC) in variousgrades under the designations, among others, Avicel RC and Avicel CL,which comprise co-processed microcrystalline cellulose andcarboxymethylcellulose sodium.

Recognizing the unacceptability of CMC in food ingredients in certainwell-populated countries, McGinley in U.S. Pat. No. 4,263,334 avoids theuse of CMC in a colloidal microcrystalline cellulose by using acombination of additives consisting of a first ingredient which is acarbohydrate sweetner, e.g., sucrose, dextrose, or hydrolyzed cerealsolids, and a second ingredient which is a hydrocolloid, e.g., guar gum,locust bean gum, gum arabic, sodium alginate, propylene glycol alginate,carrageenan, gum karaya, or xanthan gum.

Another MCC-based stabilizing agent is described by Tuason et al. inU.S. Pat. No. 5,366,742. This agent is prepared by mixing colloidal MCCwith sodium alginate in water and then adding a soluble calcium salt tothe slurry in an amount which deposits a sodium, calcium alginatecomplex on the surface of the MCC to provide barrier coating properties.After homogenization, the slurry is spray dried. The resultingstabilizing agent may be redispersed in water by use of high shearmethods which appear to break the calcium alginate crosslinks, thusallowing dispersion to occur. However, in order to disperse thisstabilizing agent using minimal agitation, it is necessary to provide acalcium sequestrant to preferentially react with the calcium in thesodium, calcium complex, thereby solubilizing the alginate.

Not all hydrocolloids when coprocessed with MCC in accordance with priorart processes provide effective barrier coating properties to thespray-dried powder that is produced. In U.S. Pat. No. 5,192,569 McGinleyet al. describe the coprocessing of MCC and a galactomannan gum, e.g.,locust bean or guar gum. Prior to spray drying, the MCC is attrited andis, therefore, colloidal. However, the flocculated product is claimed tobe comprised of spherical particles ranging in size from 0.1 to 100microns. In Example 1 for instance, spray dried powder has a particlesize range of 5-70 microns. Reconstitution or rehydration of thiscoprocessed material requires high shear conditions. In compositionshaving 15 weight % or more of the galactomannan gum, high sheardispersion of the spray-dried material results in fibrous particles.Either the spherical aggregates or the fibrous material is particularlyeffective in providing fat-like properties to foodstuffs.

U.S. Pat. No. 6,391,368 (Tuason et al.) discloses a compositioncomprising attrited colloidal microcrystalline wetcake which iscoprocessed with iota carrageenan and dried. The composition is preparedby the following process:

(a) subjecting hydrolyzed cellulose alone to attrition to make colloidalmicrocrystalline cellulose;(b) dispersing said colloidal microcrystalline cellulose in water heatedto a temperature above the solubility temperature of the dry iotacarrageenan to be coprocessed with said colloidal microcrystallinecellulose;(c) adding the dry iota carrageenan to the heated dispersion ofcolloidal microcrystalline cellulose and mixing the components, creatinga slurry;(d) homogenizing said slurry; and(e) drying said slurry to produce a coprocessed powder.

U.S. Pat. No. 6,037,380 (Venables et al) discloses a compositioncomprising microcrystalline cellulose, a relatively water insolubleattriting aid and, optionally a protective colloid. The compositions areprepared by the following process:

(a) blending together unattrited microcrystalline cellulose, anattriting agent which is relatively insoluble in water and optionally aprotective colloid;(b) subjecting the blend to high shear wet grinding for a time and undershear forces sufficient to reduce the particle size of themicrocrystalline cellulose, and(c) recovering the resulting ultra fine microcrystalline cellulosecomposition.

U.S. Pat. No. 6,117,474 (Kamada et al.) discloses a compositioncontaining a fine cellulose and a water-insoluble calcium material. Thecompositions are prepared by cogrinding an aqueous suspension ofcellulose particles and calcium particles. A water soluble gum and/orhydrophilic substance may be incorporated in order to preventre-aggregation of the fine cellulose and water-insoluble calciummaterial upon drying.

U.S. Pat. No. 6,270,830 (Kamada et al.) discloses a stabilizer for meatproducts comprising fine cellulose and a gelling agent. The stabilizermay contain a potassium or calcium salt such as insoluble calciumcarbonate, to control gelling.

SUMMARY OF THE INVENTION

In accordance with the present invention, a method has now been foundfor preparing a colloidal microcrystalline cellulose/hydrocolloidcomposition in which the hydrocolloid has a heterogeneous distributionof linkages and is more intimately mixed with and closely bound to themicrocrystalline cellulose than has previously been possible. Thisresult is accomplished by shearing a high solids mixture of themicrocrystalline cellulose and the hydrocolloid by vigorously kneadingin the presence of an anti-slip agent.

The composition of this invention may be the moist attritedmicrocrystalline cellulose/hydrocolloid solid recovered from thekneading process; or it may be the dried residue thereof prepared byremoving moisture from the moist solid, the latter being preferred forstorage, shipment and subsequent use in preparing microcrystallinecellulose based dispersions. The compositions have a mean particle size,when measured as described below, of less than about 10 microns.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention improved compositions areprovided comprising microcrystalline cellulose and a hydrocolloid. Thecompositions are prepared by (a) combining microcrystalline cellulosewetcake, a hydrocolloid and an anti-slip agent prior to uniform swellingof the hydrocolloid, and (b) shearing the combination.

The resulting compositions are characterized by a mean particle sizesmaller than has previously been achievable in MCC/hydrocolloidcompositions and a unique particle size distribution depending upon thehydrocolloid(s) employed.

The Hydrocolloid

Any hydrocolloid that will impart an increased surface charge when usedin combination with microcrystalline cellulose to produce colloidalmicrocrystalline cellulose compared to colloidal microcrystallinecellulose alone may be employed in the compositions of the presentinvention. These hydrocolloids include: seaweed polysaccharides such ascarrageenan, agar, furcellaran, alginate and alginate derivatives suchas propylene glycol alginate and monovalent salts of alginates such asthe potassium and sodium salts, plant gums including galactomannans suchas guar, locust bean gum, and tara; carboxymethyl guar, carboxymethyllocust bean gum; glucomannans such as konjac; tamarind seed;polysaccharide; pectin; karaya; acacia; tragacanth; bacterialpolysaccharides such as xanthan and pullulan; gellan and wellan;cellulose gums; alkyl cellulose ethers including hydroxypropylmethylcellulose, hydroxyethyl cellulose, hydroxymethyl cellulose andhydroxypropyl cellulose; and mixtures thereof. The carrageenans mayinclude mu, kappa, kappa-2, nu, iota, lambda, theta and mixturesthereof. The carrageenan may be processed with no, low, or high levelsof alkali. The carrageen may include refined, semi-refined, or unrefinedgrades and mixtures thereof. Preferred hydrocolloids include alginatesand carrageenans. Of these, iota carrageenan and sodium alginate areespecially preferred. Blends of hydrocolloids may be employedparticularly blends of iota carrageenan or sodium alginate and a minorportion of other hydrocolloids such as xanthan or pectic substances solong as the anti-slip agent can interact sufficiently to retardhydration of the hydrocolloid blend in the presence of themicrocrystalline cellulose wetcake to enable sufficient mechanicalenergy transfer under shearing to produce the co-attrited colloidalMCC/hydrocolloid.

Preferred results are achieved with natural hydrocolloids As used herein“natural” means present in or produced by nature and includeshydrocolloids recovered from a biological source such as plants orbacteria or microbial fermentation.

The Microcrystalline Cellulose

Any microcrystalline cellulose may be employed in the compositions ofthe present invention. Suitable feedstocks include, for example, woodpulp such as bleached sulfite and sulfate pulps, corn husks, bagasse,straw, cotton, cotton linters, flax, kemp, ramie, fermented cellulose,etc.

The amounts of microcrystalline cellulose and hydrocolloid may be variedover a wide range depending upon the properties desired in the finalcomposition. For most applications the ratio should be equal to from50/50 to 90/10 more preferably from 70/30 to 85/15 parts by weight.

The Anti-Slip Agent

The anti-slip agent is a non-lubricant material which functions incombination with the hydrocolloid. The anti-slip agent is employed in anamount sufficient to reduce slippage of the product admixture in thework zones of the equipment during processing, ie. between the rotatingscrew elements as well as between the extruder screw elements and theextruder barrel itself in a twin screw extruder during mechanicalprocessing of the admixture.

For use in the present invention the anti-slip agent may be anyinorganic salt which is essentially completely soluble in water. Aqueoussoluble inorganic salts which may be used include, for example, sodiumchloride, potassium chloride, calcium chloride, calcium lactate, calciumtartrate, calcium citrate, calcium monophosphate and magnesium chloride.Of these divalent salts are preferred. Calcium chloride is especiallypreferred.

The amount of inorganic salt depends upon the valency of the salt andthe hydrocolloid involved. The minimum amount is that which issufficient to produce a non-slippery environment with sufficientfriction to transform the MCC aggregates into a colloidal form. If toomuch salt is used this results in too much friction, increasing thetemperature thereby resulting in degradation of the hydrocolloid. Ingeneral an amount of from about 0.8% to about 3.0% by weight based onthe total weight of solids may be used. In one embodiment which usessodium alginate as the hydrocolloid and calcium chloride as theinorganic salt the amount of calcium chloride salt added is within therange 0.8% to 2.0% by weight preferably 1.0% to 1.5% for an 85:15 weightratio of microcrystalline cellulose to alginate. In another embodimentwhich uses iota carrageenan as the hydrocolloid and calcium chloride asthe inorganic salt, the added calcium chloride salt is within the range1.0% to 3.0% by weight, preferably 2.0 to 2.5% for an 85:15 ratio ofmicrocrystalline cellulose to carrageenan. Some amount of the saltgenerally remains in the final composition. When a divalent salt, suchas calcium is used, the amount of divalent cation, CA++ is from about0.18 to 3.5% based on the total weight of the powdered composition. Thisincludes any amount of calcium ions associated with the hydrocolloidemployed and may, therefore, be higher than the amount of ions in theanti-slip agent employed in the process. The amount of cation present isdetermined by the atomic absorption test method described below.

Process

In one embodiment the process of the present invention uses as thestarting material a hydrolyzed microcrystalline cellulose wetcake which,as indicated above, contains 40-60% by weight water. The hydrocolloid inthe form of a dry powder is added to the wetcake with mixing. Only alimited amount of water is available to wet, and swell, the hydrocolloidpowder in the high solids mixture of microcrystalline cellulose wetcakeand added hydrocolloid powder. After the hydrocolloid begins tohydrate—i.e., begins to wet and swell, a solution of the inorganic saltis added. It is an important aspect of the present invention that thesalt addition occurs prior to uniform wetting and swelling of thehydrocolloid powder. However, the order of addition of the components isnot narrowly critical and it is possible, for example, to add theinorganic salt solution to the MCC prior to addition of thehydrocolloid. In either case, the resulting combination is thensubjected to a shear force (such as in a twin screw extruder) tovigorously knead the mixture and comminute the microcrystallinecellulose aggregates. As used herein shear force refers to an actionresulting from applied force that causes or tends to cause twocontiguous parts of a mixture to slide relative to each other in adirection generally parallel to their plane of contact. When sufficientsalt has been added, the hydrocolloid microcrystalline cellulose mixtureno longer responds in a slippery manner but is capable of transferringthe shear force applied to the mixture as mechanical energy to communitethe microcrystalline cellulose aggregates. The amount of force appliedmust be sufficient to force association between the microcrystallinecellulose particles and the hydrocolloid.

If insufficient salt is added, the mixture remains slippery and theshear force is primarily dissipated as mechanical energy by slidingaction rather than transferred to comminute the microcrystallinecellulose aggregates. If too much salt is added, the resistance to shearis very high and the hydrocolloid in the mixture is subject todegradation due to localized heating.

The resulting sheared material is dispersed in water, homogenized andspray dried to produce the final composition of the present invention.

Most conveniently the present invention utilizes as one of the startingmaterials a hydrolyzed cellulose wetcake (i.e., the undried massproduced when a source of cellulose, preferably alpha cellulose in theform of pulp from fibrous plant materials, has been treated with amineral acid and then washed to remove the acid and by-products)generally containing about 40 to about 60 percent moisture to which ahydrocolloid is added. An anti-slip agent such as an aqueous solution ofa soluble salt is added to the mixture of the microcrystalline cellulosewetcake and hydrocolloid before the hydrocolloid has had an opportunityto uniformly swell. The mixture of partially hydrated hydrocolloid andmicrocrystalline cellulose particles is then subjected to high solidsshearing wherein the partially swollen hydrocolloid facilitatesattrition of the microcrystalline cellulose to provide colloidalparticles. If the hydrocolloid were allowed to uniformly swell prior toshearing, the swollen hydrocolloid would be too slippery to be processedand there would be insufficient energy transfer during shearing toprovide the necessary particle-to-particle abrasion forces required toreduce the microcrystalline particles to a consistent sub-micron sizeduring the attrition step. In preparation of the wet blend, the moisturecontent may be adjusted as desired to produce the consistency desiredfor attrition of the blend and adjusted as needed during attrition tomaintain the desired consistency. In a preferred embodiment the moisturepresent in the wetcake is generally sufficient. The use of excess wateris to be avoided as it will tend to reduce the particle-to-particleabrasion forces which are necessary to reduce the microcrystallinecellulose particles to a consistent sub-micron size.

The wet blend is then attrited preferably as a high-solids wet blendunder high shear high solids mixing conditions, in which themicrocrystalline cellulose is ground into ultra-fine sub-micron sizedparticles which on dispersion are colloidally stable. The colloidalstability is further facilitated by inclusion of the protectivehydrocolloid.

The protective hydrocolloids may perform one or more of severalfunctions. They act as a barrier between and/or around themicrocrystalline cellulose particles, presumably by attaching to orreplacing the hydrogen bonding forces between them, and thus form abarrier between such particles to prevent them from hornifying. Secondlythey act as dispersion aids to facilitate dispersion and rehydration ofthe microcrystalline cellulose particles when dried solid compositionsof microcrystalline cellulose are redispersed. In addition, they mayhelp in suspending and/or altering the rheological properties of thesuspension.

Reduction of microcrystalline cellulose to colloidal particle size ispreferably carried out by high solids, wet shearing of the blend ofmicrocrystalline cellulose, inorganic salt solution and protectivecolloid. The use of a standard extruder, preferably with multiplescrews, is a preferred means for reducing microcrystalline celluloseparticle size. Other standard equipment may also be used for wetshearing operations, such as planetary mixers, for example Hobart mixersand roll mills, particularly those having three or more rolls. It isimportant that the equipment used provide high shearing action andprovide intense rubbing, abrasive action on the microcrystallinecellulose, for example by forcing the mixture through passages oflimited cross section such as those found in perforated plates ofextruders and various other mixing equipment, or other passages oflimited clearance such as between rolls of roller mills. The extrusionprocess is preferred for its ease of operation in high solids, highthroughput processing and for its efficacy in yielding very fineparticles of microcrystalline cellulose.

In the process of this invention, the first step comprises blendingtogether unattrited microcrystalline cellulose and the hydrocolloid. Theanti-slip agent is added prior to high shear kneading. As indicatedabove it is also possible to combine the microcrystalline cellulose andthe anti-slip agent prior to addition of the hydrocolloid.

The wet blend is then subjected to high shear kneading for a time andunder shear forces sufficient to reduce the microcrystalline celluloseto a particle size in which about 80% to 100%, advantageously about 90%to 100%, of the microcrystalline cellulose has a particle size notgreater than 1 micrometer and is colloidally stable when dispersed inaqueous media. The hydrocolloid is closely bound to the microcrystallinecellulose.

The moist attrited microcrystalline cellulose composition resulting fromthe extrusion or other suitable kneading process may be recovered andthen dispersed as a stabilizer/suspending agent for suspension anddispersions and/or may be further processed, dried and then dispersedfor such uses. The further processing steps, if utilized, may involvepreparing an initial dispersion, homogenizing the resulting dispersion,drying it, for example, by spray drying or other suitable means, all ofwhich are within the skill of the art.

Depending on the starting ingredients and the ratios in which they areemployed, compositions of this invention thus comprise an ultra-fineattrited microcrystalline cellulose composition comprising an anti-slipagent and microcrystalline cellulose particles which have a particlesize as described above and a protective hydrocolloid, in which theweight ratio of microcrystalline cellulose to protective colloid is inthe range of about 50:50 to about 90:10, preferably from 70:30 to 85:15.

The ultra fine colloidally stable microcrystallinecellulose/hydrocolloid product of this invention is utilized indispersions, emulsions, suspensions and the like in an amount of fromabout 0.05-15 weight percent, advantageously 0.03 to 5 weight percent,preferably from about 0.05-3 weight percent, and is used as a filler orbulking agent, in an amount of about 1-15 weight percent, based on thefinal product. For food applications, 0.05-15 weight percent maysuitably be used.

Composition

The products prepared by the present process differ from those preparedby prior art processes. As compared to the products prepared by theprocesses of the Kamada et al and Venables et al patents discussed abovein which a solid attriting aid is used, the products of the presentinvention exhibit molecular distribution of the inorganic saltthroughout the hydrocolloid/microcrystalline composition rather than inthe form of fine inorganic particulates. The heterogeneous distributionof linked hydrocolloid closely bound with the colloidal microcrystallinecellulose provides for unique rheological behavior of the re-dispersedpowder. As compared to the process of Tuason et al. discussed above inwhich the components of pre-attrited microcrystalline cellulose andsodium alginate are simply combined in a slurry, such that the alginateis uniformly hydrated when the soluble divalent metal salt is added,then subjected to high shear e.g., in a homogenizer, and dried to entrapthe colloidal microcrystalline cellulose particles within a calciumalginate gel matrix, the products of the present invention exhibit finercolloidal particle size with tightly bound and heterogeneous linkedalginate polymer due to high solids wet shearing of the microcrystallinecellulose wetcake and the partially swollen hydrocolloid in the presenceof the antislip agent.

The compositions of the present invention are “coattrited” meaning thatthe MCC and the hydrocolloid are combined prior to application of highshear forces to the combination. They are characterized by physicalproperties not heretofore achievable.

All of the compositions contain at least 70% MCC and have a meanparticle size of less than 10 microns. As used herein particle sizerefers to the value obtained by the test procedure described below.Preferred compositions have a particle size distribution (againdetermined by the test procedure described below) which depends on thehydrocolloid(s) used. Specifically,

-   (i) when the hydrocolloid is a carrageenan at least about 50% of the    particles have a particle size less than about 3.5 microns,-   (ii) when the hydrocolloid is a hydrocolloid other than a    carrageenan at least about 30% of the particles have a particle size    less than about 3.5 microns, and-   (iii) when the hydrocolloid is a combination of a carrageenan and    another hydrocolloid at least about 20% of the particles have a    particle size less than about 3.5 microns.

The products of the present invention can be used where colloidal gradesof MCC are currently used including retortable chocolate beverages, bakestable bakery fillings, frozen desserts, aerated food systems, and saladdressings. These products are particularly suited for UHT-processedbeverages, dairy and nondairy, such as those containing fresh soyprotein or soy isolate, cocoa powder, and nutritional additives such asvitamins and minerals. In addition, this new colloidal MCC productextends product functionality to open up new opportunities for colloidalMCC. New product applications are due to the new and/or improvedproperties of the product. These include the following properties:reduced reactivity with proteins, improved freeze-thaw stability in lowpH cultured dairy products, improved suspension functionality with widerprocess tolerance in UHT prepared beverages, improved texturemodification in UHT cream products and improved heat stability in bakeryfillings. Due to their reduced reactivity with proteins, thecompositions can be used at low levels but with more process latitudesince the range of effectiveness is broader so the amount is notnarrowly critical. Dry mix products (instant sauces, gravies, soups,instant cocoa drinks, etc.), low pH dairy systems (sour cream/yogurt,yogurt drinks, stabilized frozen yogurt), baked goods (pie/pastryfillings), beverages (citrus flavored drinks, etc.), and productslabeled all are areas of application. Other uses are as a bulking agentin non-aqueous food systems e.g., peanut butter, etc. and in lowmoisture food systems, as an excipient for chewable tablets, tastemasking drug actives such as APAP, aspirin, ibuprofen, etc., suspendingagent, and controlled release agent in pharmaceutical applications.These new colloidal products are also suitable for use as a deliverysystem for flavoring agents and nutraceutical ingredients in food,pharmaceutical and agricultural applications (including animal feed),and as a direct compression sustained release agent. They are alsouseful in pharmaceutical dosage forms such as tablets, films andsuspensions. In addition they may be used as thickeners, in foams,creams and lotions for personal care (skin, hair) applications, and assuspending agents, for use with pigments and fillers in ceramics,colorants, cosmetics, and oral care and in industrial applications suchas ceramics, delivery systems for pesticides including insecticides andin other agricultural products.

In order to illustrate the present invention the following examples areset forth.

In the Examples, the following standard materials and test procedureswere used:

I. “Mean Particle Size” and Particle Size Distribution—

A dispersion was prepared with a Waring Blender (700 series), using a1,000 ml bowl, at a speed of 18,000 to 19,000 rpm controlled by aPowerstat transformer which permits increasing of the Waring Blenderspeed gradually to avoid splashing.

1. Weigh 16 g (±0.01 g) of powder in a weigh boat.2. Weigh 587±1 g distilled or deionized water in a 500 ml graduate andpour it into the blender bowl.3. Slowly bring the blender speed up to about 30 volts with thetransformer. Add the powder to the center of the water, taking care toprevent it from adhering to the sides of the bowl.4. After the addition of the powder replace the bowl lid and mix for 15seconds.5. After 15 seconds mixing, increase the volts to 115, as quickly aspossible, and mix at 115 volts for 2 minutes.6. Store the dispersion in a 500 ml Nalgene bottle.

The mean particle size and the particle size distribution were measuredusing a Horiba LA-910 (available from Horiba Instruments, Inc., Irvine,Calif.) static light scattering particle size distribution analyzer.

II. Ca++ and Calcium Chloride Content—Measured by the Following CalciumFlame Atomic Absorption Test Method:

Procedure: A. Standard/Blank Preparation:

1. Prepare a 5% lanthanum chloride solution as follows:

-   -   Accurately weigh 12.5 g of lanthanum chloride 7-hydrate and        transfer into a 250 mL volumetric flask containing approximately        100 mL of 0.1 N hydrochloric acid (HCl). Place in an ultrasonic        bath for 10 minutes, remove and allow to cool to room        temperature then fill to volume with 0.1 N HCl.        2. Prepare a 100-ppm calcium stock standard as follows:    -   Transfer 10.0 mL of commercial 1,000-ppm calcium standard        (Thermo Orion #922006, VWR #34183-182) into a 100 mL volumetric        flask containing approximately 50 mL of 0.1NHCL, shake well and        fill to volume with 0.1 N HCl.        3. Prepare 2, 4, 7, 10, 13 and 16-ppm calcium standards as        follows:    -   Transfer 2, 4, 7, 10, 13 and 16 mL of the 100-ppm calcium stock        standard into labeled 100 mL volumetric flasks containing 10 mL        of 5% lanthanum chloride solution and approximately 50 mL of 0.1        N HCl. Shake well and fill to volume with 0.1 N HCl.        4. Prepare a blank solution as follows:    -   Transfer 10 mL of 5% lanthanum chloride solution into a 100 mL        volumetric flask and fill to volume with 0.1 N HCl.

B. Sample Preparation:

1. Perform loss on drying (LOD) testing on all samples to determinepercent moisture.2. Transfer 200 mg of MCC sample into a labeled 100 mL volumetric flaskwith approximately 50 mL of 0.1 N HCl.3. Place in an ultrasonic bath for 30 minutes, remove and allow to coolto room temperature.4. Add 10 mL of 5% lanthanum chloride solution and fill to volume with0.1 N HCl.5. Centrifuge at 3,500 rpm/5 minutes and transfer supernatant into a13×100 mm culture tube.6. Dilute as necessary with 0.1 N HCl containing 0.5% lanthanum chlorideto achieve results within the 2 to 16 ppm calcium range of the standardcurve.

C. Analysis:

-   -   Instrument: Perkin-Elmer Analyst 300 atomic absorption        spectrometer.    -   Lamp: Calcium    -   Wavelength: 422.8 nm    -   Signal Measurement Time Average    -   Flame Type: Air/Acetylene    -   Oxidant Flow: 10.0 L/min.    -   Fuel Flow: 3.0 L/min    -   Slit Width: 0.7    -   Read Time: 5 seconds    -   Delay Time: 28 seconds    -   Calibration: Linear

D. Calculation:

Weight of calcium (mg)=ppm calcium·100·Dilution Factor/1000%Calcium=(weight of calcium (mg)/sample weight (mg)·(100−% LOD/100))·100%Calcium chloride=% calcium·(110.98/40.08)

III. Bake (Heat) Stability—bake stability was determined by measuringshape retention by the following procedure. Shape retention is definedas the capacity of a fruit filling preparation to retain its initialshape and volume after being baked for a definite amount of time at agiven temperature. A defined volume of fruit filling preparation (approx35 g) is placed in a standardized ring (3.5 cm), which is placed on apaper graduated with concentric circles. The fruit filling is baked fora defined period of time at a specific temperature (usually 10 minutesat 400° F.) in a ventilated oven. After the heat treatment, the spreadof the fruit filling is measured. The spread is expressed in apercentage [(Final diameter−initial diameter)/initial diameter×100].

Example I

In a 5 gal Hobart mixer, 1,744.9 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging from 38-44% was admixed with90.8 grams of iota carrageenan to obtain an MCC to iota carrageenansolids ratio of 90/10 parts by weight. 27.7 grams of a 30% solution ofCaCl₂ was added and mixed for several minutes. The admixture was passedthrough a co rotating twin-screw extruder several times to shear theadmixture and comminute the microcrystalline aggregates. The resultingconsistency of the extrudate was not slippery thereby enabling it to besubjected to a high work profile which facilitated the formation ofcolloidal microcrystalline cellulose particles.

418.6 grams of the MCC/iota carrageenan extrudate was dispersed in2,581.4 grams of distilled water at about 160° F. The resulting slurrywas passed through a Manton Gaulin homogenizer at 2,500 psi and spraydried to form a powder. The spray drying was performed as follows: Thehomogenized slurry was fed to a 3 foot (0.9144 m) Bowen spray dryerutilizing nozzle atomization 0.1 inch (0.00254 m) opening. The slurrywas fed to the dryer by means of a variable feed Moyno pump at a rate toprovide the desired outlet temperature. The operating inlet/outlet airtemperature of the spray dryer was about 195° C./95° C. The spray dryingconditions were regulated depending upon feed properties such asviscosity and resulting dried product characteristics and subsequentyield.

A water dispersible colloidal MCC powder having a very fine colloidalparticle size distribution was obtained. Particle size analysis by laserlight diffraction showed that the powder had a mean particle size of5.33 microns and a particle size distribution of 85% of the particlesless than 3.5 microns. When dispersed in deionized water, its 2.6%dispersion exhibited an initial Brookfield viscosity of 1,100 cps and aviscosity of 1,150 cps when retested after 24 hours.

Comparative Example I No Anti-Slip Agent

In a 5 gal Hobart mixer, 1,744.9 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging from 38-44% was admixed with90.8 grams of iota carrageenan to obtain an MCC to iota carrageenansolids ratio of 90/10 parts by weight. The admixture was passed througha co rotating twin-screw extruder several times to shear the admixtureand comminute the microcrystalline aggregates. The resulting consistencyof the extrudate was very slippery and thus, the necessary friction orwork profile in the extruder was not obtained to mechanicallydisintegrate the MCC aggregates to produce colloidal particles.Microscopic evaluation of the extrudate revealed that the MCC particleswere large and unattrited thus, they were not colloidal.

Example II

In a 5 gal Hobart mixer, 1,550.5 of microcrystalline cellulose (MCC)wetcake with a solids content ranging from 38-44% was admixed with 136.6grams of iota carrageenan to obtain an MCC to iota carrageenan solidsratio of 85/15 parts by weight. 40 grams of a 30% solution of CaCl₂ wasadded and mixed for several minutes. The admixture was passed through aco rotating twin-screw extruder several times to shear the admixture andcomminute the microcrystalline aggregates. The resulting consistency ofthe extrudate was not slippery thereby enabling it to be subjected to ahigh work profile which facilitated the formation of colloidalmicrocrystalline cellulose particles.

584.4 grams of the MCC/iota carrageenan extrudate was dispersed in2,415.6 grams of distilled water at about 160° F. The resulting slurrywas passed through a Manton Gaulin homogenizer at 2,500 psi and spraydried to form a powder. The spray drying was performed as follows: Thehomogenized slurry was fed to a 3 foot (0.9144 m) Bowen spray dryerutilizing nozzle atomization 0.1 inch (0.00254 m) opening. The slurrywas fed to the dryer by means of a variable feed Moyno pump at a rate toprovide the desired outlet temperature. The operating inlet/outlet airtemperature of the spray dryer was about 195° C./95° C. The spray dryingconditions were regulated depending upon feed properties such asviscosity and resulting dried product characteristics and subsequentyield.

A water dispersible colloidal MCC powder having a very fine colloidalparticle size distribution was obtained. Particle size analysis by laserlight diffraction showed that the powder had a mean particle size of4.27 microns. When dispersed in water, its 2.6% dispersion exhibited aninitial viscosity of 1,700 cps and a set-up viscosity of 2,450 cps whenretested after 24 hours suggesting an effective interaction that is, agood gel network, between the MCC and the iota carrageenan.

A 0.5% level of this 85/15 microcrystalline cellulose/iota carrageenanprovided a stable cocoa suspension in a retortable nutraceuticalchocolate beverage and a UHT processed soy protein-based chocolatebeverage.

Comparative Example II Insufficient Level of Anti-Slip Agent

In a 5 gal Hobart mixer, 1,539.3 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging from 38-44% was admixed with127.6 grams of iota carrageenan to obtain an MCC to iota carrageenansolids ratio of 85/15 parts by weight. 25.0 grams of a 30% solution ofCaCl₂ was added and mixed for several minutes. The admixture was passedthrough a co rotating twin-screw extruder several times to shear theadmixture and comminute the microcrystalline aggregates. The resultingconsistency of the extrudate was still slippery and thus, the necessaryfriction or work profile in the extruder was not obtained tomechanically disintegrate the MCC aggregates into ultra fine particles.Microscopic evaluation of the extrudate revealed that the MCC particleswere large and unattrited thus, they were not colloidal. The amount ofcalcium salt added was insufficient to compete with the carrageenan forwater hence, allowing the carrageenan gum to solvate further.

Example III

In a 5 gal Hobart mixer, 1,915.3 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging from 38-44% was admixed with387.1 grams of iota carrageenan to obtain an MCC to iota carrageenansolids ratio of 70/30 parts by weight. 75 grams of a 30% solution ofCaCl₂ was added and mixed for several minutes. The admixture was passedthrough a co rotating twin-screw extruder several times to shear theadmixture and comminute the microcrystalline aggregates. The resultingconsistency of the extrudate was not slippery thereby enabling it to besubjected to a high work profile which facilitated the formation ofcolloidal microcrystalline cellulose particles.

309.3 grams of the MCC/iota carrageenan extrudate was dispersed in2,690.7 grams of distilled water at about 160° F. The resulting slurrywas passed through a Manton Gaulin homogenizer at 2,500 psi and spraydried to form a powder. The spray drying was performed as follows: Thehomogenized slurry was fed to a 3 foot (0.9144 m) Bowen spray dryerutilizing nozzle atomization 0.1 inch (0.00254 m) opening. The slurrywas fed to the dryer by means of a variable feed Moyno pump at a rate toprovide the desired outlet temperature. The operating inlet/outlet airtemperature of the spray dryer was about 195° C./95° C. The spray dryingconditions were regulated depending upon feed properties such asviscosity and resulting dried product characteristics and subsequentyield.

A water dispersible colloidal MCC powder having a very fine colloidalparticle size distribution was obtained. When dispersed in water, its2.6% dispersion exhibited an initial viscosity of 2,000 cps and a set upviscosity of 12,900 cps when retested after 24 hours suggesting aneffective interaction that is, a good gel network between the MCC andthe iota carrageenan.

A sweetened yogurt prepared using 0.25 wt % of this 70/30microcrystalline celluose/iota carrageenan powder had a smoothconsistency and glossy texture. When subjected to freeze/thawconditions, the 70/30 MCC/iota-based product was stable as it maintainedits smooth and glossy texture.

Example IV

In a 5 gal Hobart mixer, 1,947.9 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging from 38-44% was admixed with171.7 grams of sodium alginate to obtain an MCC to sodium alginatesolids ratio of 85/15 parts by weight. 33.3 grams of a 30% solution ofCaCl₂ was added and mixed for several minutes. The admixture was passedthrough a co rotating twin-screw extruder several times to shear theadmixture and comminute the microcrystalline aggregates. The resultingconsistency of the extrudate was not slippery thereby enabling it to besubjected to a high work profile which facilitated the formation ofcolloidal microcrystalline cellulose particles.

258.6 grams of the MCC/alginate extrudate was dispersed in 2,741.4 gramsof distilled water at about 160° F. The resulting slurry was passedthrough a Manton Gaulin homogenizer at 2,500 psi and spray dried to forma powder. The spray drying was performed as follows: The homogenizedslurry was fed to a 3 foot (0.9144 m) Bowen spray dryer utilizing nozzleatomization 0.1 inch (0.00254 m) opening. The slurry was fed to thedryer by means of a variable feed Moyno pump at a rate to provide thedesired outlet temperature. The operating inlet/outlet air temperatureof the spray dryer was about 195° C./95° C. The spray drying conditionswere regulated depending upon feed properties such as viscosity andresulting dried product characteristics and subsequent yield.

A water dispersible colloidal MCC powder having a very fine colloidalparticle size distribution was obtained. Particle size analysis by laserlight diffraction showed that the powder had a mean particle size of6.04 microns. When dispersed in water, its 2.6% dispersion exhibited aninitial viscosity of 1,675 cps and a set up viscosity after 24 hours of1,725 cps.

Example V 85/15 MCC/A-H Kappa Carrageenan

In a 5 gal Hobart mixer, 1,938.1 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging 38-44% was admixed with168.9 grams of fully modified calcium kappa carrageenan to obtain thedesired MCC to kappa carrageenan solids ratio. 100 grams of a 15%solution of CaCl₂ was added and mixed for several minutes. The admixturewas passed through a co rotating twin-screw extruder several times toshear the admixture and comminute the microcrystalline aggregates. Theresulting consistency of the extrudate was not slippery thereby enablingit to be subjected to a high work profile which facilitated theformation of colloidal microcrystalline cellulose particles.

331.1 grams of the MCC/kappa carrageenan extrudate was dispersed in2,268.9 grams of distilled water at about 160° F. 1.35 grams of K₂CO₃was added and mixed for several minutes to adjust the pH to 8.0-8.5. Theresulting slurry was passed through a Manton Gaulin homogenizer at 2,500psi and spray dried to form a powder. The spray drying was performed asfollows: The homogenized slurry was fed to a 3 foot (0.9144 m) Bowenspray dryer utilizing nozzle atomization 0.1 inch (0.00254 m) opening.The slurry was fed to the dryer by means of a variable feed Moyno pumpat a rate to provide the desired outlet temperature. The operatinginlet/outlet air temperature of the spray dryer was about 195° C./95° C.The spray drying conditions were regulated depending upon feedproperties such as viscosity and resulting dried product characteristicsand subsequent yield.

A water dispersible colloidal MCC powder having a very fine particlesize distribution in which 50% of the particles were below 3.5 micronswas obtained. When dispersed in water, its 2.6% dispersion exhibited aninitial viscosity of 725 cps and a set-up viscosity of 3,350 cps.

In a UHT processed nutraceutical chocolate beverage application, the85/15 MCC/kappa carrageenan used at 0.10% provided a stable cocoasuspension.

Example VI 70/30 MCC/HM Pectin

In a 5 gal Hobart mixer, 1,676.5 of microcrystalline cellulose (MCC)wetcake with a solids content ranging 38-44% was admixed with 100 gramsof a 30% solution of CaCl₂ and mixed for several minutes. 324.1 grams ofhigh methoxyl (HM) pectin was added to obtain the desired MCC to HMpectin solids ratio. The admixture was passed through a co rotatingtwin-screw extruder several times to shear the admixture and comminutethe microcrystalline aggregates. The resulting consistency of theextrudate was not slippery thereby enabling it to be subjected to a highwork profile which facilitated the formation of colloidalmicrocrystalline cellulose particles.

315.1 grams of the MCC/iota carrageenan extrudate was dispersed in2,684.9 grams of distilled water at about 160° F. 3 grams of K₂CO₃ wasadded and mixed for several minutes to adjust the pH to 5.0-5.4. Theresulting slurry was passed through a Manton Gaulin homogenizer at 2,500psi and spray dried to faun a powder. The spray drying was performed asfollows: The homogenized slurry was fed to a 3 foot (0.9144 m) Bowenspray dryer utilizing nozzle atomization 0.1 inch (0.00254 m) opening.The slurry was fed to the dryer by means of a variable feed Moyno pumpat a rate to provide the desired outlet temperature. The operatinginlet/outlet air temperature of the spray dryer was about 195° C./95° C.The spray drying conditions were regulated depending upon feedproperties such as viscosity and resulting dried product characteristicsand subsequent yield.

A water dispersible colloidal MCC powder having a very fine particlesize distribution was obtained. Particle size analysis by laser lightdiffraction of its 2.6% dispersion showed that it had a median particlesize of 6.56 microns and a mean particle size of 8.98 microns. Whendispersed in water, its 2.6% dispersion exhibited an initial viscosityof 675 cps and a set-up viscosity of 975 cps.

In a drinkable yogurt application, the 70/30 MCC/HM pectin used at 0.33%produced good stabilization.

Example VII 70/30 MCC/PGA

In a 5 gal Hobart mixer, 1,089.8 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging 38-44% was admixed with197.2 grams of propylene glycol alginate (PGA) with a high degree ofesterification (DE) to obtain the desired MCC to PGA solids ratio. 65grams of a 30% solution of CaCl₂ was added and mixed for severalminutes. The admixture was passed through a co rotating twin-screwextruder several times to shear the admixture and comminute themicrocrystalline aggregates. The resulting consistency of the extrudatewas not slippery thereby enabling it to be subjected to a high workprofile which facilitated the formation of colloidal microcrystallinecellulose particles. 312.0 grams of the MCC/PGA extrudate was dispersedin 2,688 grams of distilled water at about 160° F. The resulting slurrywas passed through a Manton Gaulin homogenizer at 2,500 psi and spraydried to form a powder. The spray drying was performed as follows: Thehomogenized slurry was fed to a 3 foot (0.9144 m) Bowen spray dryerutilizing nozzle atomization 0.1 inch (0.00254 m) opening. The slurrywas fed to the dryer by means of a variable feed Moyno pump at a rate toprovide the desired outlet temperature. The operating inlet/outlet airtemperature of the spray dryer was about 195° C./95° C. The spray dryingconditions were regulated depending upon feed properties such asviscosity and resulting dried product characteristics and subsequentyield.

A water dispersible colloidal MCC powder having a very fine particlesize distribution was obtained. Particle size analysis by laser lightdiffraction of its 2.6% dispersion showed that it had a median particlesize of 5.87 microns and a mean particle size of 7.40 microns.

In a drinkable yogurt application, the 70/30 MCC/PGA used at 0.35%produced good stabilization.

Example VIII 75/15/10 MCC/IOTA Carrageenan/HM Pectin

In a 5 gal Hobart mixer, 1,818.8 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging 38-44% was admixed with163.7 grams of iota carrageenan to obtain the desired MCC to iotacarrageenan solids ratio. 200 grams of a 15% solution of CaCl₂ was addedand mixed for several minutes. The admixture was passed (1 pass) througha co rotating twin-screw extruder. 108 grams of high methoxyl (HM)pectin was added to the MCC/Iota carrageenan admixture. This was passedthrough the extruder several times to shear the admixture and comminutethe microcrystalline aggregates. The resulting consistency of theextrudate was not slippery thereby enabling it to be subjected to a highwork profile which facilitated the formation of colloidalmicrocrystalline cellulose particles.

343.6 grams of the MCC/iota carrageenan/HM pectin extrudate wasdispersed in 2,656.4 grams of distilled water at about 160° F. Theresulting slurry was passed through a Manton Gaulin homogenizer at 2,500psi and spray dried to form a powder. The spray drying was performed asfollows: The homogenized slurry was fed to a 3 foot (0.9144 m) Bowenspray dryer utilizing nozzle atomization 0.1 inch (0.00254 m) opening.The slurry was fed to the dryer by means of a variable feed Moyno pumpat a rate to provide the desired outlet temperature. The operatinginlet/outlet air temperature of the spray dryer was about 195° C./95° C.The spray drying conditions were regulated depending upon feedproperties such as viscosity and resulting dried product characteristicsand subsequent yield.

A water dispersible colloidal MCC powder having a very fine particlesize distribution with 21% of the particles below 3.5 microns wasobtained. When dispersed in water, its 2.6% dispersion exhibited aninitial viscosity of 725 cps and a set-up viscosity of 925 cps.

In a sweetened yogurt product application, the 75/15/10 MCC/iotacarrageenan/HM pectin used at 0.25% level produced a sweetened yogurtthat had a smooth consistency and glossy texture. When subjected tofreeze/thaw conditions, the MCC/iota carrageenan/HM pectin product wasstable as it maintained its smooth and glossy texture

Example IX 75/15/10 MCC/Iota Carrageenan/Xanthan Gum

In a 5 gal Hobart mixer, 1,818.8 grams of microcrystalline cellulose(MCC) wetcake with a solids content ranging 38-44% was admixed with163.7 grams of iota carrageenan to obtain the desired MCC to iotacarrageenan solids ratio. 200 grams of a 15% solution of CaCl₂.2H₂O wasadded and mixed for several minutes. The admixture was passed (1 pass)through a co rotating twin-screw extruder. 107.2 grams of xanthan gumwas added to the MCC/Iota carrageenan admixture. This was passed throughthe extruder several times to shear the admixture and comminute themicrocrystalline aggregates. The resulting consistency of the extrudatewas not slippery thereby enabling it to be subjected to a high workprofile which facilitated the formation of colloidal microcrystallinecellulose particles.

343.5 grams of the MCC/iota carrageenan/HM pectin extrudate wasdispersed in 2,656.6 grams of distilled water at about 160° F. Theresulting slurry was passed through a Manton Gaulin homogenizer at 2,500psi and spray dried to form a powder. The spray drying was performed asfollows: The homogenized slurry was fed to a 3 foot (0.9144 m) Bowenspray dryer utilizing nozzle atomization 0.1 inch (0.00254 m) opening.The slurry was fed to the dryer by means of a variable feed Moyno pumpat a rate to provide the desired outlet temperature. The operatinginlet/outlet air temperature of the spray dryer was about 195° C./95° C.The spray drying conditions were regulated depending upon feedproperties such as viscosity and resulting dried product characteristicsand subsequent yield.

A water dispersible colloidal MCC powder having a very fine particlesize distribution with 26% of the particles below 3.5 microns wasobtained. When dispersed in water, its 2.6% dispersion exhibited aninitial viscosity of 450 cps and a set-up viscosity of 700 cps.

Example X

A fruit filling composition was prepared from the following components.All amounts are in parts by weight. In this Example, the followingmaterials were used:

GRINSTED LA410—low ester amidated pectin available from Danisco.COLFLO 67—modified cook-up starch from waxy maize available fromNational Starch.Raspberry concentrate—20% fruit solids available from IFF.MCC/Sodium Alginate—prepared as described in Example IV above.

Component Amount GRINSTED LA410 5 MCC/Sodium Alginate 5 Water 420 Sugar337 COLFLO 67 starch 20 Raspberry concentrate 200 Potassium sorbate 1 3% calcium lactate in water 5 50% citric acid in water 7 Brix solids43% Hot viscosity, cP 13,800 Bake stability 11% Gel strength, grams 75

The GRINSTED LA410 and MCC/Sodium Alginate were dry blended and thendispersed in water using high shear mixing for 7 minutes. The sample wasthen heated to 90° C. while stirring. A dry blend of COLFLO 67 starch,sugar and potassium sorbate was added with stirring. After cooking for10 minutes to ensure that the starch was dispersed, the Raspberryconcentrate was added and the sample re-heated and held for 10 minutesat from 87° C. to 90° C. Brix was determined using a refractometer. Thecalcium lactate and citric acid solutions, were added sequentially. Thefruit filling was poured into jars. Hot viscosity was measured using aBrookfield RVT #4 spindle, 10 rpm after 1 minute. The samples werecooled to room temperature and refrigerated prior to testing for gelstrength and bake stability.

1. A composition comprising (a) at least 70% by weight microcrystallinecellulose, and (b) a hydrocolloid wherein the composition has a meanparticle size of less than about 10 microns
 2. A composition as claimedin claim 1, wherein (i) when the hydrocolloid is a carrageenan at leastabout 50% of the particles have a particle size less than about 3.5microns, (ii) when the hydrocolloid is a hydrocolloid other than acarrageenan at least about 30% of the particles have a particle sizeless than about 3.5 microns, and (iii) when the hydrocolloid is acombination of a carrageenan and another hydrocolloid at least about 20%of the particles have a particle size less than about 3.5 microns.
 3. Acomposition as claimed in claim 1 having a Ca++ content of from 0.18 to3.5% by weight based on the total weight of the composition.
 4. Acomposition as claimed in claim 1 wherein the amount of hydrocolloid isequal to from 15% to 30% by weight based on the total weight ofhydrocolloid and microcrystalline cellulose.
 5. A composition as claimedin claim 1 wherein the hydrocolloid is a carrageenan.
 6. A compositionas claimed in claim 1 wherein the hydrocolloid is an alginate.
 7. Acomposition as claimed in claim 1 wherein the amount of microcrystallinecellulose is equal to from 70% to 85% by weight based on the totalweight of hydrocolloid and microcrystalline cellulose.
 8. A compositionas claimed in claim 1 further comprising a water soluble inorganic salt.9. A composition as claimed in claim 8 wherein the amount of inorganicsalt is equal to at least 1% by weight based on the total weight of thecomposition.
 10. A composition as claimed in claim 7 wherein theinorganic salt is selected from the group consisting of sodium chloride,calcium chloride, calcium lactate, calcium tartrate, and calciummonophosphate.
 11. A composition as claimed in claim 7 wherein theinorganic salt is calcium chloride.
 12. A composition as claimed inclaim 1, wherein the microcrystalline cellulose and the hydrocolloid arecoattrited.
 13. A process for preparing a microcrystalline cellulosecomposition, said process comprising: (a) forming a high solids mixtureof microcrystalline cellulose, a hydrocolloid and an anti-slip agent and(b) kneading the mixture.
 14. A process as claimed in claim 13 whereinthe microcrystalline cellulose is combined with the hydrocolloid beforethe anti-slip agent is added.
 15. A process as claimed in claim 13wherein the microcrystalline cellulose is combined with the anti-slipagent before the hydrocolloid is added.
 16. The process of claim 13 inwhich the hydrocolloid is selected from the group consisting ofcarrageenans and alginates.
 17. The process of claim 13 in which thehydrocolloid is a carrageenan.
 18. The process of claim 13 in which thehydrocolloid is an alginate.
 19. The process of claim 13 in which theanti-slip agent is an aqueous solution of an inorganic salt.
 20. Theprocess of claim 19 in which the inorganic salt is a divalent salt.21.-31. (canceled)